Process for breaking petroleum emulsions



Patented Aug. 10, 1943 PROCESS FOR BREAKING PETROLEUM EMULSIONS Allen, Long CaliL, assignor to Gwynne Beach,

Petrolite Corporation, Ltd., St. Louis, Mo., a

corporation of Delaware PPlication May 27, 1942,

N Drawing.

Serial No. 444,764

. 11 Claims.

This invention relates primarily to the treatment of emulsions of mineral oil and water; such as petroleum emulsions, for the p p se of separating the oil from the water.

This invention is a continuation in part of my copending application, Serial No. 392,099, flled on May 6, 1941-. Reference is also made to my copending applications Serial Nos. 444,761, 444,- 762, 444,763, 444,765, 444,766 and 444,767, filed May 27, 1942.

One object of my invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to .as "cut 0 "roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughgout the oil which constitutes the continuous. phase of the emulsion, my process being particularly adapted to the resolution of crude oil emulsions of the kind obtained in connection with the treatment or the flooding of subterranean oil-hearing strata by means of aqueous agents or the like.

Another object of my invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsiflcation and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganicsalts, from .pipeline oil.

The process which constitutes one feature of my present invention consists in subjecting a petroleum emulsion of the water-in-oil type to the action of a demulsifying agent, thereby causing the emulsion to break and separate into its component puts of oil and water or brine when the emulsion is permitted to remain in a quiescent state after treatment, or is subjected to other equivalent separatory procedure. The demulsifying agent employed in my process consists of a poly-carboxylic-acid-reacted polymeric sub-rubbery sulfur-converted ester of a p yhydric alcohol, and more particularly an ester in which there are present at least 2 acyl radicals derived from unsaturated high molal monocarboxylie detergent-forming acids having at least 8, and not more than 32, carbon atoms each.

It is known that when elemental sulfur-is heated with a reactive detergent-forming carboxylic acid, for example with oleic acid, the sulfur adds at the double bond in the oleic acid chain or radical. Where the oleic acid is employed in combination with a polyhydric alcohol,

such as glycerol, as for example in triolein which is the tri-glyceride of,0leic acid, the reaction apparently does not stop with the formation'of a simple addition product. Instead, as discussed in the literature, e. g., Knight and Stamberger, J. Chem. Soc. London, 1928, pp, 2791-8, triolein takes up additional sulfur atoms,-possibly even tied in throughthe glyceral radical. Also, it is probable that the several fatty acid radicals present are also linked through sulfur atoms.

Compare comparable reactions involving more reactive sulfur di-chloride, and particularly the duction of the molecular weight, loss of the elasticproperties, and apparently a return to a simpler In my process, I make no addition product. claim to the use of the simple unpolymerized addition product of sulfur and an unsaturated high molal monocarboxylic detergent-forming acid having at least 8, and not more than 32, carbon atoms, typified by sulfurized oleic acid, I make no claim to the use of the free detergentforming carboxylic acid and sulfur alone in preparing my reagent: but I employ the acid only -in combination with a polyhydric alcohol compound containing two or more alcoholiform hydroxyl groups in the form of an ester of-such acid and such polyhydric alcohol.

The compound containing the two or more alcoholiform hydroxyl groups may be a simple polyhydric alcohol, such for example as glycerol orethylene glycol, or it maybe a condensed polyhydric alcohol, like polyglycerol, di-ethylene glycol, di-glycerol, or tri-glycerol. In addition to the above polyhydric alcohols, I may also use mannitan, sorbitan, pentaerythritol, and dipentaerythritol. I may use ether alcohols so long' as they have two or more hydroxyl groups in the molecule, 1. e., -(polyhydric'alcohcls in which a carbon atom chain is interrupted at least once by oxygen, as exemplified by di-ethylene glycol previously mentioned). They are all characterized by containing two or more alcoholiform hydroxyl groups and by having the power to form esters with an unsaturated high molal monocarboxylic detergent-forming acid having at least 8, and not more than 32, carbon atoms.

Resinous and similar materials are sometimes classified as thermoplastic, thermo-setting, and element-convertible. The expression elemeat-convertible refers particularly to plastic coatings or drying oils in which hardening apparently is due to conversion into a new compound or composition by action of an element used, often oxygen. Thus, drying oils are often referred to as being oxygen-convertible." For practical purposes, the only other element finding wide application for this purpose is sulfur. Hence, certain products, and particularly certain oils, are referred to as sulfur-convertible, meaning that they react with sulfur or sulfur dichloride to get polymeric materials, rubbery masses, factice, or the like.

The unsaturated high molal detergent-forming monocarboxylic acids employed by me in preparing my reagent are characterized by having a carbon atom chain, which I shall denote as R, containing at least 8 carbon atoms and not more than 32 carbon atoms, and which must contain at least one unsaturated bond, 1. e., at least one ethylene linkage. Such acids are sometimes referred to as ethylenic.

The acyl radical may, of course, have present other non-functional groups, such as hydroxyl groups, acyl-oxy groups, etc. It is only necessary that the presence of such groups does not detract from (a) the detergent-forming ability of the acids and (b) their susceptibility to sulfur conversion. Suitablility of substituted acids is indicated by very simple tests. For instance, saponification with caustic potash, caustic soda, or the like, must yield a soap or soap-like material. Secondly, if the detergent-forming properties have not been eliminated by the presence of this substituent atom or radical, then it is only necessary to determine that susceptibility to sulfur conversion is still present. Such test is obviously the same procedure as is herein described for preparing my reagent, except that it is conducted on a small scale in the laboratory. If the substituted acid or ester, which has been previously determined to have detergent-formin properties, also shows sulfur conversion susceptibility, it is, of course, the obvious functional equivalent of the unsubstituted or unmodified acids or esters herein described and may be used with equal or even greater effectiveness.

Such high molal acids may be obtained from various sources, such as oils, fats, and waxes; or one may use petroleum acids, rosin acids, and the like. Petroleum acids include naturally-occurring naphthenic acids and also acids obtained by the oxidation of hydrocarbons and waxes. Rosin acids include abietic acid, pyroabietic acids, and the like. Saturated acids, such as saturated fatty acids, saturated naphthenic acids, saturated oxidized petroleum acids, etc., can frequently be converted into an unsaturated acid by halogenization, followed by a reaction of the kind exemplified by the internal Wurtz reaction.

My preference is to use unsaturated fatty acids, due to their low cost and ready availability. One need not use a single fatty acid, but may use the mixture obtained by saponification of a naturally-occurring oil or fat. For instance, special reference is made to the fatty acids which occur naturally in olive oil, castor oil, peanut oil, cottonseed oil, fish oils, corn oil, soybean oil, linseed oil and many other naturally-occurring oils. Rapeseed oil, for example, contains appreciable proportions of trierucin, the tri-glyceride of erucic acid. I have found it useful to prepare my reagent.

As has been previously pointed out, the high molal acids are used in the form of the polyhydri alcohol ester having at least 2 such high molal acid radicals present. Since it is my preference to use the naturally-occurring fatty acids, it obviously follows that my preference is to use the naturally-occurring glycerides. However, if desired, one can obtain the high molal acids from any source and esterify such acids with various polyhydric alcohols, such as the glycols. in the conventional manner to produce suitable esters which may or may not have a free or unreacted alcoholiform hydroxyl group present. The fatty acid di-glycerides typify these esters which contain a free or unreacted alcoholiform hydroxyl group (in the residue of the polyhydric alcohol, glycerol) The fatty acid tri-glycerides do not possess this free alcoholiform hydroxyl. Both types of glyceride, for example, are suitable for my purpose, provided the fatty acid present satisfies the above-expressed requirements. The manufacture of such esters is so well known that no description is required in the present instance.

One may select esters of the mixed type and such mixed esters may even contain acyl radicals which either are not high molal in character or are not unsaturated, i. e., ethylenic in nature. For instance, diolein may be reacted with one mol of acetic acid or one mol of stearic acid to give an ester which would be satisfactory for the present purpose. As an example of a modified ester which may serve, reference is made to triacetylated triricinolein.

In those instances where an ester of a high molal detergent-forming acid of the type previously described is first reacted with a poly-carboxylic acid before any other step in the preparation of my reagent, possession of one or more alcoholiform hydroxyl groups is required to confer reactivity. If the ester be a tri-glyceride, for example, the detergent-forming acid must contain an alcoholiform hydroxyl group. Ricinoleic acid would satisfy the requirement, in this case. If the ester be a dl-glyceride, the free alcoholiform hydroxyl group present in the glyceryl radical is suflicient to permit the di-glyceride to meet the above requirement.

I have found that, in addition to naturallyoccurring fatty acids, addition and substitution products of fatty acids obtained by the action of chemical reagents on fatty acids-which latter modify fatty acids bear a simple genetic relationship to the parent fatty acids from which they were derived-are also useful for making my reagent, so long as they are in part unsaturated, i. e., possess some double bond, as shown by possession of an Iodine Number of appreciable magnitude, or, in those cases where a detergentforming carboxylic acid is first reacted with a poly-carboxylic acid in producing my reagent, only so long as they possess an alcoholiform hydroxyl group, also.

Instead of employing natural poly-esters of reactive detergent-forming carboxylie acids in preparing my reagent, I may use synthetic esters obtained by esterifying one or more reactive detergent-forming carboxylic acids with a polyhydric alcohol of the kind heretofore recited and described in a conventional esteriflcation reaction, such as reacting the alcohol with the acid or acids in various molecular proportions in the presence of, for example, dry hydrogen chloride.

The compound produced by the interaction of a polyhydric alcohol of the above kind and a reactive detergent-forming carboxylic acid of the -above kind will be termed a poly ester" in the present description. In all instances, it must contain two or more radicals or residues derived from reactive detergent-forming carboxylic acids which may be the same ordifferent acids; and it contains one or more radicals or residues derived from polyhydric alcohols. Di-glycerides of unsaturated fatty acids are examples of poly esters, just as are the naturally-occurring tri-glycerides of unsaturated fatty acids.

The reaction of elemental sulfur with such a poly ester is at first one of simple addition of sulfur at the double bond in the chain R of an acid residue in such poly ester to form a sulfurized derivative which does not differ greatly from the parent ester in properties. However, when the reaction is allowed to proceed at controlled temperatures, there is obtained a complex poly meric sulfurized product of high molecular weight, which is semi-elastic and highly viscous and which approaches the consistency of rubber, depending on the time and temperature of reaction, and the proportions of reactants employed.

The nature of the chemical changes which take place is, to the best of my knowledge, not yet fully understood. I have referred above to a literature reference which suggests various mechanisms for the polymerization process. Without attempting to express exactly the composition of the reagents I employ, I desire to use those polymeric sulfurized bodies obtained as above recited which have a consistency short of rubber. Accordingly, I have termed the subrubbery to denote a range of polymerization between the simple sulfur addition products, on one hand, and the non-usable rubbers produced on super-polymerization, on the other. Such sub-rubbery products are capable of dissolving in solvents to produce fluid reagents which are practicable to be used commercially.

After preparing the polymeric sub-rubbery sulfurized derivative of a poly ester of a reactive detergent-forming carboxylic acid as above re- 50 cited, I may then react said derivative with a poly-carboxylic acid of the following kind.

Poly-carboxylic acids include phthalic acid,

oxalic acid, maleic acid, succinic acid, citraconic acid, citric acid, glutaric acid, etc., all of which 55 contain two or more carboxyl groups, -COOH, in the molecule. I prefer to use dibasic acids having 8 carbon atoms or less. In preparing my reagent, the acid itself may be employed, or it may be preferable to employ the acid inthe form of its anhydride. For example, phthalic anhydride is available at a reasonable price in a state of high technical purity. In some instances, the anhydride shows little or no tendency to produce undesirable secondary reactions that phthalic acid shows. Therefore, in the case of phthalic acid, I have found it desirable to employ the anhydride instead of the acid in preparing my reagent. In addition to the simple poly-carboxylic acids and their anhydrides, I have found their functional equivalents, e. g., the substituted polycarboxylic acids like chlorophthalic acid equally useful in preparing my reagent.

The reagent which I use may be prepared by ester of (a) a reactive detergent-forming carboxylic acid and (b) a polyhydrlc alcohol with a polycarboxylic acid of the above described kind to produce a complex condensation product.

In preparing my preferred reagent, 125 parts by weight of castor oil are heated to 180 C. Fifteen parts by weight of sulfur are added, and

the mixture is stirred continuously for to v minutes at 188 to 190 0., or until a sample withdrawn from the reaction vessel and cooled is semi-elastic and transparent, indicating the complete absence of unreacted sulfur. To this sulfurized body there is then added 19 parts by weight of phthalic anhydride. The temperature is reduced somewhat by such addition, but is still sufliciently high to produce the desired reaction between the sulfurized castor oil body and the phthalic anhyride.

As a second example of a reagent which I prefer to use, the following is given: 298 parts of ricinoleic acid are mixed with 46 parts by weight of glycerol, and the mixture is agitated and heated in the presence of dry hydrogen chloride gas at a temperature in excess of 100 C. for a period of time suficient to produce an ester. (1 have found that reacting 6 hours at 150 C. is satisfactory to accomplish this.) If this procedure is tedious or undesirable, the di-glyceride of ricinoleic acid may. be prepared in any other desired manner. For example, di-glycerides are commonly prepared by treating two mols of the tri-glyceride with one mol of glycerol in the presence of an alkaline catalyst. The ester so pro-- duced is mixed with 15% of its weight of elemental sulfur, and the agitation and heating are continued until all the sulfur is assimilated and a clear transparent product is obtained, as shown by a test on glass. The product has considerable viscosity and a semi-elastic nature. This product is then mixed with 40 parts by weight of oxalic acid at as low a temperature as practicable to prevent decomposition or sublimation of said oxalic acid. I prefer to employ tempera- .tures between 110 and 123 C. Agitation is continued for a period of time until the reaction is complete. Usually, heating may be discontinued on addition of the oxalic acid, the reaction bei completed by the time the temperature has dropped to atmospheric levels.

. As a thirdexample, substitute diolein for the diricinolein prepared and used in. the second example, Just recited.

diolein.)

Other esters of unsaturated fatty acids or other reactive detergent-forming carboxylic acids of the 60 ample; I have used cottonseed 011 instead of castor oil in making certain examples of my reagent and have found it to be useful therein, However, when cottonseed oil is used, the reaction is usually not as smooth as when castor oil is employed;

Also, it is usually found that longer heating is required to produce the desired reagent of optimum properties. It is, therefore, preferable to use castor oil rather than cottonseed oil, so far as I am now aware. Also. other poly-carboxylic acids may be used instead of the phthalic anhydride and the oxalic. acid of the above examples.

The stages of polymerization and condense. tion and the elastic properties of the resulting reacting the Po y u bery sulfurized products may be altered by varyin the tem- (In this instance, the oxalic acid reacts through the free alcohoiiform' hydroxyl group of the glyceryl radical of the perature of the reaction, the time of the reaction, or the proportions of reactants employed. or any combination of these variables. I have found that the most effective reagents are those obtained by reacting 100 parts by weight of the ester with from to 17 parts by weight of sulfur, controlling the temperature to avoid the evolution of hydrogen sulfide so far as is practicable, and employing a time sufficient to obtain highly polymerized products which are, however, still soluble in petroleum distillates; and then reacting such sulfurized bodies with phthalic anhydride using approximately 10 to 20 parts by weight of the phthalic anhydride.

While the foregoing description has shown products obtained by subjecting a sulfurized poly ester to the action of a poly-carboxylic acid, I have also found that in some instances the procedure may be modified in that the poly-carboxylic acid may be reacted with the poly ester first; and, the poly-carboxylic-acid-reacted poly ester may be subsequently sulfurized to produce highly useful products. For example, where the poly ester contains hydroxylated detergent-forming acids like ricinoleic acid, reaction readily takes place between a carboxyl group of the polycarboxylic acid and a hydroxyl group of the hydroxylated detergent-forming acid. Also, if the poly ester contains one or more free alooholii'orm hydroxyl groups from any other source, as for example'the free hydroxyl group of the glyceryl radical in a di-glyceride, the poly ester will be reactive with the poly-carboxylic acid used. My invention, therefore, goes equally to the use of polymeric sub-rubbery derivatives produced by sulfurizing poly-carboxylic-acid-reacted poly esters of (a) reactive detergent-forming acids and (b) polyhydric alcohols in such instances where direct reaction between the poly-carboxylic acid and the poly ester is capable of taking place. The final products are broadly similar when sulfurization occurs before reacting the poly-carboxylic acid and the poly ester, and when sulfurization occurs after such reaction of the poly-carboxylic acid and the poly ester, although the products are not necessarily of identical structural configuration.-

In other words, I have found that it is possible to prepare reagents of broadly similar composition and of equally valuble properties by varying the above-recited method of preparation as follows: Instead of reacting a poly-carboxylic acid with a sulfurized poly ester of a detergentforming acid and a polyhydric alcohol, as above recited, I have reacted, for example, the same proportions of castor oil and phthalic anhydride, and have subsequently added the same proportion of sulfur with heat and stirring to produce my reagent. This alternative procedure may in certain instances offer advantages over that recited hereinbefore, in that it may be more adaptable toplant operations or the product so obtained may be detectably superior to that pro duced in the other-recited procedure. My invention, therefore, contemplates a reagent produced either by reacting a poly-carboxylic acid and a sulfurized poly ester or sulfurizing the reaction product of a poly-carboxylic acid and a poly ester (to the extent that the latter procedure is possible, as outlired above).

The final product, comprising a poly-carboxylic-acid-reacted polymeric sub-rubbery sulfurized poly ester of (a) a reactive detergent-forming carboxylic acid and (b) a polyhydric alcohol, will in some instances exhibit a free carboxyl group, COOH, depending on the proportions of poly-carboxylic acid added and the procedure employed in preparing the final product, all as recited above. Any acidity due to such free carboxyl group may be allowed to remain in the final product, or it may be neutralized by a. suitable neutralizing agent, such as a metallic hydroxide or ammonia, or by a suitable alcohol in an esteriflcation reaction. a

The complex polywcarboxylic acid reacted polymeric sub-rubbery 'suli'urized compound obtained as recited above may be diluted with one or more solvents" or diluents to improve its viscosity or othercharacteristics, as desired. Examples of suitable diluents are isopropanol, mineral spirits, benzol, etc,

In practising my process, the improved treating agent hereinbefore described is usually employed in the proportion of one part of reagent to from 2,000 to 20,000 parts of petroleum emul sion, either in concentrated form or after diluting as desired with a. suitable vehicle or diluent or solvent. I desire to point out that the superiority of my reagent or demulsifying agent is based on its ability to treat or break certain emulsions more advantageously and at a lower cost than is possible with otheravailable demulsifiers or conventional mixtures thereof.

In practising my process, a reagent of the kind. above described is brought into contact with or is caused to act upon the emulsion to be treated in any of the various ways or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with some other demulsifying procedure, such as the electrical dehydration process. I,

While I have described in detail the preferred embodiment of my invention, it is understood that the materials employed, the proportions of ingredients, the arrangements of steps, and the details of procedure may be variously modified without departing from the spirit of the subjoined claims.

I claim:

1. A process for breaking petroleum emulsions of the water-in-oil type. characterized by sub- .iecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted sub-rubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfur-conversion containing at least 2 unsaturated high molal detergent-forming monocarboxylic acid radicals having at least 8 carbon atoms and not' more than 32 carbon atoms each.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted subrubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfur conversion containing at least 2 unsaturated high molal detergent-forming monocarboxylic acid radicals having at least 8 carbon atoms and not more than 32 carbon atoms each; and said ester prior to sulfur-conversion being free from any unreacted hydroxyl radical as part of the alcoholic residue.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted subrubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfur converany unreacted hydroxyl sion containing at least 2 unsaturated fatty acid radicals having at least 8 carbon atoms and not more than 32 carbon atoms each; and said ester prior to sulfur-conversion being free from any unreacted hydroxyl radical as part of the 2.100- holic residue.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted subrubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfur-conversion containing at least 2 monoethylenic fatty acid radicals having at least 8 carbon atoms and not more than 32 carbon atoms each; and said ester prior to sulfur-conversion being free from radical as part of the alcoholic residue.

5. A process for of the water-in-oil type, jecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted sub-rubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfurconversion containing at least 2 radicals derived from monoethylenic fatty acids having 18 carbon atoms each; and said ester prior to sulfurconversion being free from any unreacted hydroxyl radical as part of the alcoholic residue.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted sub-rubbery polymeric sulfur-converted glycerol ester; said ester prior to sulfur-conversion containing 3 monoethylenic fatty acid radicals having 18 carbon atoms each; and said ester prior to sulfur-conversion being free from any unrebreaking petroleum emulsions characterized by sub-- .fier comprising acted hydroxyl radical as part of the alcoholic residue.

7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a poly-carboxylic-acid-reacted sub-rubbery polymeric sulfur-converted triricinolein.

8. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsia phthalic-acid-reacted subrubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfur-conversion containing at least 2 unsaturated high molal detergent-forming monocarboxylic acid radicals having at least 8 carbon atoms and not more than 32 carbon atoms each.

9. A process for breaking petroleum emulsions of the water-in-oil type, characterized bysubjecting the emulsion to the action of a demulsifier comprising a rubbery polymeric sulfur-converted tri-ricinolein.

10. A process for breaking petroleum emul sions of the water-in-oil type. characterized by subjecting the emulsion to the action of a demulsifier comprising an oxalic-acid-reacted subrubbery polymeric sulfur-converted polyhydric alcohol ester; said ester prior to sulfur-conversion containing at least 2 unsaturated hi h molal detergent-forming monocarboxylic acid radicals having at least 8 carbon atoms and not more than 32 carbon atoms each; 7

11. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising an oxalic-acid-reacted subrubbery polymeric sulfur-converted tri-ricinolein.

QWYNNE ALLEN.

phthalic-acid-reacted sub-- 

